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RESEARCH PRODUCT

Discrete Dinuclear Complexes and Two‐Dimensional Architectures from Bridging Polynitrile and Bipyrimidine (bpym) Ligands: Syntheses, Structures and Magnetic Properties of [M 2 (bpym)(dcne) 4 (H 2 O) 2 ] (M = Mn II , Co II ) and [M 2 (bpym)(dcne) 4 (H 2 O) 4 ]·2H 2 O (M = Fe II , Cu II ) (dcne − = [(CN) 2 CC(O)OEt)] − )

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One-pot reactions in aqueous solutions of the polynitrile anion dcne− {2,2-dicyano-1-ethoxyethenolate = [(CN)2CC(O)OEt)]−] with the MII ions (M = Mn, Fe, Co, Cu) in the presence of bpym (2,2′-bipyrimidine) afford the first mixed dcne/bpym compounds [M2(bpym)(dcne)4(H2O)2] (1: M = Mn; 2: M = Co) and [M2(bpym)(dcne)4(H2O)4]·2H2O (3: M = Fe; 4: M = Cu). The new compounds have been characterized by IR spectroscopy and X-ray crystallography. Compounds 1 and 2 are isostructural, with each metal ion being located in an MN5O pseudo-octahedral environment with three N atoms coming from three dcne− ligands, two nitrogen atoms from bpym and one oxygen atom from a water molecule. The extended structures of 1 and 2 are best described as dcne-bridged zigzag chains of MII ions running along the [100] direction; connections of these chains in the [010] direction, by the bis(chelating) bpym ligand, afford 2D structures. Compounds 3 and 4 are isostructural, and consist of discrete dinuclear units involving MN4O2 octahedrally coordinated MII ions bridged by bis(bidentate) 2,2′-bipyrimidine and terminal dcne ligands. Magnetic measurements for the 2D compounds 1 and 2 exhibit maxima in the χm vs. T plots (at about 4.5 K for 1 and about 20 K for 2) which are characteristic of weak antiferromagnetic exchange interactions between the high-spin metal centres. While the dinuclear iron complex 3 presents a similar behaviour (maximum in χm vs. T plot at 12 K), the antiferromagnetic exchange interactions are stronger in the copper complex 4. Fits of magnetic data for compounds 1, 3 and 4 with appropriate models led to J values of −0.6, −1.5 and −99.0 cm−1 respectively. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)